Curable cyanoalkylaromatic compositions

ABSTRACT

Hydroxyaromatic compounds are amido-alkylated or cyano-alkylated to form the corresponding compounds by: 
     (a) heating said compounds with an alkylating agent in the presence of water and a catalyst, e.g., benzyltrimethylammonium chloride; 
     (b) adding an alkaline agent, e.g., NaOH, to the heated mixture of (a); and 
     (c) continuing to heat the resulting mixture until the corresponding amido- or cyano-alkylated compound is formed. 
     Fully or partially amido-alkylated compositions are useful in the preparation of copolymers with epoxy resins.

This application is a division of Ser. No. 901,842, filed Aug. 29, 1986,now U.S. Pat. No. 4,798,908, which is a division of Ser. No. 723,971,filed Apr. 16, 1985, now U.S. Pat. No. 4,632,965, and acontinuation-in-part of Ser. No. 301,170, filed Sept. 11, 1981, now U.S.Pat. No. 4,517,131.

BACKGROUND OF THE INVENTION

This invention relates to the catalytic cyano-alkylation oramido-alkylation of hydroxyaromatic reactants and to compounds madethereby.

Compounds containing terminal amide or nitrile moieties are useful asprecursors to carboxylic acids. Several routes to amido-alkylatedhydroxyaromatic compounds are known. For example, a three-step method ofsynthesizing a di(amido-methylated)hydroquinone derivative is disclosedin Chemical Abstracts, Vol. 64, 17566e (1966). This three-step methodinvolves reacting hydroquinone with chloroacetic acid, reacting theresulting carboxylic acid with thionyl chloride, and then reacting thenext resulting acid chloride with ammonia to get p-phenylenedioxydiacetamide. It is also known to convert hydroquinone to a diester,which is then subjected to aminolysis to yield p-phenylenedioxydiacetamide. Diss. Pharm. Pharmacol., Vol. 20, No. 6, 589-597 (1968).

U.S. Pat. No. 3,716,583 discloses, among other things, a non-catalyticmethod of forming amido-alkylated bisphenolic derivatives. The firststep requires reacting a bisphenolic compound with an alkaline agent toform an alkaline salt. Then, an α-halogenated aliphatic acid derivativeis added to start a condensation reaction, thereby forming anarylenedioxy dialkyleneamide.

Arylenedioxy dialkylenenitriles have also been prepared in the past.U.S. Pat. No. 4,061,777 discloses the non-catalytic reaction ofα-chloroacetonitrile with substituted phenols to get the correspondingphenoxyacetonitrile. Similarly, alcohols were reacted withα-chloroacetonitrile in the presence of KOH and benzene to givealkoxynitriles. Chemical Abstracts, Vol. 85, 159369d (1976).Arylenedioxy dialkylenenitriles are also available via Michael additionof acrylonitrile to hydroxyaromatic compounds, however, yields aremodest.

Heretofore, a high yield process for the catalytic monophasicamido-alkylation or cyano-alkylation of hydroxyaromatic compounds hasnot been disclosed.

SUMMARY OF THE INVENTION

In one aspect, the present invention is a process for alkylatinghydroxyaromatic compounds by contacting a hydroxyaromatic reactant withan alkylating agent, as hereinafter defined, in the presence of acatalyst and a solvent, and subsequently adding an alkaline agent to themixture under conditions sufficient to form the corresponding aromaticamide or nitrile. Surprisingly, the practice of said process requiresonly one step to convert a hydroxyaromatic reactant to the correspondingamide or nitrile in an aqueous, monophasic system. More importantly, thepractice of said process produces products in yields much superior tothe yields obtainable by the methods of the prior art, and obviates theneed to employ a non-aqueous solvent. With few exceptions, the productsproduced are solids and are easily filtered from the reaction medium.

In another aspect, this invention is the discovery of novel compoundswhich may be prepared by the method of the present invention. Theproducts from the cyano-alkylation or amido-alkylation reactions of thisinvention are useful as chemical intermediates. Exemplary of thisutility is the reaction of the amide products in a number of well-knownreactions, such as the Hoffman degradation of amides and the hydrolysisof amides with acid or alkaline catalysis to form the correspondingcarboxylic acids. The cyano-alkylated products of this invention areeasily converted to amines by known methods and may be hydrolyzed byknown methods to form carboxylic acids.

The present invention also pertains to thermosettable compositionscomprising:

(1) an amidoalkyl aromatic compound, a partially amido-alkylatedhydroxyaromatic compound, or a mixture thereof;

(2) at least one epoxy resin; and, optionally,

(3) a suitable copolymerization catalyst.

Another aspect of the present invention pertains to the productsresulting from the copolymerization, i.e., curing, of the aforementionedthermosettable compositions.

DETAILED DESCRIPTION OF THE INVENTION

Hydroxyaromatic compounds are suitably employed in the practice of thisinvention and are aromatic or alkylaromatic compounds which bear one ormore hydroxy moieties. These compounds are generally represented by theformula Ar--OH)_(n) wherein n is at least one and Ar is a mono- orpolyvalent organic radical. For non-polymeric hydroxyaromatic compounds,Ar preferably is selected from the group consisting of: (a) arylmoieties having from 1 to 3, preferably from 1 to 2, aromatic rings;including fused ring systems, and (b) moieties of the formula ##STR1##wherein R is optional and is selected from the group consisting of S,sulfoxide, sulfone, methylene, alkylidene, such as C₁₋₃ alkylidene, O,and arylene; and wherein m and p have values independently from zero to2; and wherein X₁ and X₂ are independently selected from the groupconsisting of Cl, Br, F, alkyl, nitro, and nitrile. Examples of typicalhydroxyaromatic compounds include polyhydroxybenzenes,polyhydroxynaphthalenes, tris(hydroxyphenyl)alkanes, phenol, andbisphenol A and its alkylated derivatives. An example of a class oftypical hydroxyaromatic compounds can be represented generally by theformula: ##STR2## wherein R₅ is independently H, C₁ -C₁₀ alkyl oralkoxy, Cl or Br; and wherein Ar and n are as previously defined.Preferred non-polymeric hydroxyaromatic reactants are aromatic compoundsbearing at least two hydroxy moieties. Examples includedihydroxybenzenes, thiodiphenols, dihydroxybiphenyls, and halogenatedderivatives of bisphenol A. The most preferred non-polymerichydroxyaromatic reactants bear exactly two hydroxy moieties, e.g.,p-dihydroxybenzene, m-dihydroxybenzene, 4,4'-thiodiphenol,4,4'-dihydroxydiphenyl oxide and 3,3',5,5'-tetrabromo bisphenol A.Non-ortho isomers are preferred when the hydroxyaromatic reactant hasonly one aromatic ring. The hydroxyaromatic reactants may bear groups orsubstituents which do not interfere with the amido-alkylation orcyano-alkylation reaction. Examples of these substituents include nitro,nitrile, alkoxy, alkyl, alkenyl, Cl, Br, F and the like. Preferredhydrocarbyl substituents contain from 1 to about 4 carbon atoms. Anexample of such a hydroxyaromatic reactant is p-chlorophenol.

Hydroxyaromatic compounds may also be polymers, including oligomers,which bear one or more hydroxy moieties. Examples of polymerichydroxyaromatic reactants include phenol formaldehyde polymers, with thenovolacs being preferred, and resorcinol formaldehyde polymers.Preferred polymeric hydroxyaromatic reactants are represented by theformula: ##STR3## wherein R' is independently a divalent hydrocarbonmoiety having from 1 to about 3, preferably 1, carbon atoms or a##STR4## group, wherein z has a value of from zero to about 10,preferably from zero to 3; n' is individually selected from 0, 1 or 2;Ar' is a mono- or polyvalent organic radical selected from moietieshaving from 1 to 2 aromatic rings; and q is at least about 0.001. Morepreferably, q is from about 0.01 to about 6. The most preferredpolymeric hydroxyaromatic reactants are represented by the foregoinghydroxyaromatic formula wherein q is from about 0.1 to about 3, R' ismethylene, n' is 1, and Ar' is a hydrocarbon aromatic single ring.Mixtures of polymeric hydroxyaromatic reactants are also operable. Forexample, a polymer mixture wherein the average value of q is 0.2 is amost preferred hydroxyaromatic reactant.

The alkylating agents employed in the practice of this invention arehaloamidohydrocarbylenes or halocyanohydrocarbylenes. The preferredalkylating agents are generally represented by formula I: ##STR5##wherein X is a halogen; R₁ and R₂ are independently H or C₁ -C₁₀ alkyl;Y is --C.tbd.N or ##STR6## wherein R₃ and R₄ are independently H or C₁-C₁₀ alkyl. Preferably, X is Cl or Br, and R₁, R₂, R₃ and R₄ are H or C₁-C₃ alkyl. Examples of preferred alkylating agents include2-chloropropionamide and 2-chloropropionitrile. The most preferredalkylating agents are 2-chloroacetamide and α-chloroacetonitrile.Mixtures of alkylating agents can be employed.

The amount of alkylating agent employed is partially dependent on thenumber of hydroxy moieties on the hydroxyaromatic reactant and on thedesired degree of substitution. The alkylating agent usually is employedin an amount which will provide an alkylating agent/hydroxy moiety molarratio of from about 0.1 to about 4. Preferably this ratio will be fromabout 1 to about 3. Lower amounts of alkylating agent can be employedwhen partially amido- or cyano-alkylated products are desired as themajor product.

An alkaline agent is employed in the practice of the present inventionfor the purpose of increasing conversion to the cyano- oramido-alkylated product. The alkaline agent may be an alkali metalhydroxide or an alkaline earth metal hydroxide. Preferred alkalineagents are KOH, NaOH or mixtures thereof. Sodium hydroxide is the mostpreferred alkaline agent. The alkaline agent is typically employed inorder to provide a ratio of from about 0.1 to about 2 moles of alkalimetal hydroxide per mole of hydroxy moieties originally present on thehydroxyaromatic reactant. Preferably this ratio will be from about 1 toabout 1.5.

Water is typically employed in the process of this invention for thepurpose of providing a suitable reaction medium. This allows thereaction to be carried out in one phase and subsequently allows theremoval of the reaction product as a filterable solid, except for rarecases in which the product is a liquid as is the case when thehydroxyaromatic reactant is bisphenol A.

The catalyst may be a quaternary ammonium of phosphonium salt.Quaternary ammonium halides are preferred catalysts. Benzyltrialkylammonium halides, such as benzyltrimethyl ammonium halides, are the mostpreferred catalysts. Typically, from about 0.001 to about 0.25 moles ofcatalyst are employed per mole of hydroxy moiety of the hydroxyaromaticreactant. Preferably, from about 0.01 to about 0.10 moles of catalystare employed per mole of hydroxy moiety of the hydroxyaromatic reactant.

Catalytic quaternary salts may be bound in a polymeric support in theform of ion-exchange resins. Typical ion-exchange resins are those whichbear quaternary ammonium salts on macroporous styrene-divinylbenzeneresins. Examples of these bound quaternary salts include Dowex® MSA-1and the like. The ion-exchange resin form of catalyst is advantageous inthat it is easily recovered or, if used in a fixed bed, obviates theneed for a catalyst recovery step. It should be noted that a catalystbound in a polymeric support generally will not go into solution. Thus,for the purposes of this invention, a monophasic solution may containsolid particles of bound catalyst. Preferably, when solid particles ofbound catalyst are employed, they will be uniformly dispersed in thereaction mixture or will form a fixed bed.

The reactants may be added in any order desired, except for the alkalineagent. Preferably, the alkaline agent is added as an aqueous solution.The alkaline agent preferably is added only after the reaction mixturecontaining the hydroxyaromatic reactant, the alkylating agent, thecatalyst and the water or a portion thereof, has been heated to thedesired prereaction temperature and the aforementioned ingredients haveformed a monophasic solution. The alkaline agent may be added before amonophasic solution forms, i.e., while the aforementioned ingredientsare in the form of a slurry. At some point during the addition of thealkaline agent to a non-monophasic mixture, a monophasic solution willbe formed. Preferably, the reaction mixture is further heated for thedesired time after the alkaline agent has been added.

The reaction is preferably conducted at reflux temperatures, althoughhigher or lower temperatures may be employed if desired. The reactiontime depends on the temperature employed and usually takes between about1 and about 24 hours; preferably it takes between about 4 and about 8hours. Shorter reaction times and/or lower reaction temperaturesgenerally can be employed when partially amido- or cyano-alkylatedproducts are desired.

When the reactants, catalyst and water are properly combined underreaction conditions as hereinbefore specified, a product mixture will beformed. In most cases this mixture will contain the product in(micro)crystalline form. The solid product may be separated by directfiltration from the non-product portions of the reaction mixture.Washing of the solid product is often beneficial. In some cases theproduct will be in liquid form. Liquid products, such asdi(cyano-methylated)bisphenol A, may be recovered by conventional meanssuch as decantation or solvent extraction.

At least one component of the product mixture will be amido- orcyano-alkylated and will correspond structurally to the particularhydroxyaromatic reactant used as a starting material. The productsformed are generally represented by the formula

    Ar--(OQ).sub.n

wherein Q is independently H or --CR₁ R₂)Y with the proviso that all Qmoieties are not H; n is at least one; and Ar, R₁, R₂ and Y are aspreviously defined.

The amido-alkylated products of the present process can be cured orcopolymerized with known epoxy resins. Epoxy resins suitable for use inthe present invention are well-known and can be prepared by the knownmethods described in the Handbook of Epoxy Resins by Lee and Neville,McGraw-Hill (1967), which is incorporated herein by reference. Thisusually includes reacting a hydroxyaromatic compound with anepihalohydrin followed by dehydrohalogenation with an alkaline-actingmaterial, such as an alkali metal hydroxide, and finally recovering theresultant glycidyl ether product.

Examples of preferred epoxy resins for use in the present invention arethose represented by the formulas: ##STR7## wherein each A isindependently a divalent hydrocarbon group having from 1 to about 12,preferably from about 1 to about 6 carbon atoms, --S--, --S--S--,##STR8## and the like; each R' is as defined hereinbefore; each R_(a) isindependently hydrogen or a hydrocarbyl or hydrocarbyloxy group havingfrom 1 to about 6 carbon atoms or a halogen, preferably chlorine orbromine; m' has a value of 1 to about 100, preferably from 1 to about10; n" has a value of zero or 1; q is as defined hereinbefore; m" has avalue from zero to about 40, preferably from 0.1 to about 5; and R_(b)is independently hydrogen or a hydrocarbyl group having from 1 to about3 carbon atoms.

Suitable catalysts for curing or copolymerization of the epoxy resin andthe amidoalkyl aromatic compound, or partially amido-alkylatedhydroxyaromatic compound are described in the aforemention Handbook ofEpoxy Resins. Typical examples of said catalysts are the tertiaryamines, imidazoles, N-alkyl morpholines and tertiary alkanolamines. Apreferred catalyst is 2-methyl imidazole.

If desired, one or more curing agents can be employed herein includingthose well recognized in the art such as carboxylic acids andanhydrides, primary amines, secondary amines, substituted guanidinecompounds, hydroxyaromatic compounds, imides, and the like and mixturesthereof. Examples of such curing agents are described in theaforementioned Handbook of Epoxy Resins. The copolymerization reactionis usually conducted at a temperature of from about 20° C. to about 250°C., preferably from about 100° C. to about 200° C. for a period of fromabout 5 minutes to about 7 days, preferably from about 15 minutes toabout 4 hours.

The epoxy resin and amidoalkyl aromatic compound or partiallyamido-alkylated hydroxyaromatic compound are typically used to preparecopolymerized (cured) products by providing about a 1 to 1 mole ratio ofepoxide groups to Zerewitinoff active hydrogens, although a lower orhigher mole ratio can be employed, as is known in the art.

The epoxy resin and amidoalkyl aromatic compound or partiallyamido-alkylated hydroxyaromatic compound can be used to preparecastings, coatings, laminates, composites, encapsulations and the like,and are especially suited for use in applications requiring high solventresistance. If desired, solvent, filters, pigments, flow control agents,dyes, flame suppressants and other additives can be employed.

In the preparation of laminates or composites from the compositions ofthe present invention, suitable substrates include, but are not limitedto, woven and nonwoven fibers and/or filaments of glass, carbon,graphite, boron, aramid, asbestos, glass and carbon hybrids,combinations thereof and the like.

For the purposes of this invention, alkyl, aryl, methylene andalkylidene moieties may be substituted with other moieties which do notinterfere with the cyano-alkylation or amido-alkylation reaction.

The following examples are given to illustrate the invention and shouldnot be construed as limiting its scope. All percentages in the examplesare by weight unless otherwise indicated.

I. Variation of the Hydroxyaromatic Reactant Example 1

Six-tenths of a mole of 2-chloroacetamide, hydroquinone (0.10 mole),benzyltrimethylammonium chloride catalyst (0.04 mole), and water (25.0g) are added with stirring to a reactor under a nitrogen atmosphere. Thereactor is heated and the stirred slurry becomes a clear light brownsolution between the temperatures of 70° C.-75° C. The temperature isallowed to stabilize at 110° C., then 0.40 mole of sodium hydroxidedissolved in 25.0 g of water is added to the stirred solution. A lighttan colored slurry forms and the reaction is continued at 110° C. for atotal of 1.1 hours. The reactor is allowed to cool to room temperatureand the product is recovered as a wet filter cake. The wet crude productis slurried into 100 g of water and is heated to 100° C. It is held atthis temperature for 15 minutes. Filtration of the hot slurry isfollowed by vacuum drying, providing an 83.9 percent isolated yield ofdi(amido-methylated)hydroquinone.

Example 2

A reaction is completed using the method of Example 1 except thattetrabromobisphenol A (0.10 mole) is used in place of hydroquinone, theamount of water is increased to 50.0 g, and the reaction time isincreased to 3.0 hours. Di(amido-methylated)tetrabromobisphenol A isisolated in 99.3 percent yield.

Example 3

A reaction is done using the method of Example 1 except that1,3-dihydroxybenzene (resorcinol) (0.10 mole) is used in place ofhydroquinone and the reaction time is increased to 2.0 hours with a 112°C. reaction temperature. Di(amido-methylated)resorcinol is isolated in83.4 percent yield.

Example 4

A reaction is done using the method of Example 1 except that4,4'-thiodiphenol (0.10 mole) is used in place of hydroquinone, theamount of water is increased to 35.0 g and the reaction time isincreased to 1.2 hours with a 112° C. reaction temperature.Di(amido-methylated)4,4'-thiodiphenol is isolated in 87.6 percent yield.

Example 5

Two reactions are done using the method of Example 1 except that1,2-dihydroxybenzene (catechol) (0.10 mole) is used in place ofhydroquinone and the reaction time of the first reaction is 3 hourswhile the reaction time of the second reaction is 16 hours with a 114°C. reaction temperature. After cooling the reactor to room temperature(21° C.), the slurry is held at this temperature for 3 hours withoutfurther stirring. The filtered product is washed with the minimum ofwater required to reestablish a slurry. The slurry is then vacuum driedat 85° C. for 24 hours to a constant weight, and is then analyzed usingnuclear magnetic resonance spectroscopy. The product (18.2 g) of thefirst reaction contains 65.4 percent monoamide and 34.6 percent diamide.The second reaction provides a 98.4 percent isolated yield ofdi(amido-methylated) 1,2-dihydroxybenzene.

Example 6

One-tenth of a mole of 4,4'-dihydroxybiphenyl, α-chloroacetonitrile(0.60 mole) and 60 percent aqueous benzyltrimethylammonium chloridecatalyst (0.04 mole) are added to a reactor under a nitrogen atmosphere.The reactor is heated to 92° C. then sodium hydroxide (0.40 mole)dissolved in water (60.0 g) is added to the fine stirred slurry over a23-minute period. The initial aqueous sodium hydroxide addition inducesformation of a clear brown refluxing solution. The reaction continues at90° C. to 95° C. for a total of 80 minutes. The reactor is allowed tocool and once 70° C. to 75° C. is reached, a crystalline slurry forms.After chilling to 4° C. for 1 hour, filtration followed by multiple hotwater washing of the filter cake and vacuum drying provides thedi(cyano-methylated) product in 99.6 percent yield. The product wasanalyzed by gas chromatography and nuclear magnetic resonancespectroscopy. A sample of the di(cyano-methylated) product isrecrystallized from 1,4-dioxane providing transparent needles.

Example 7

A reaction is completed using the method of Example 6, except that4,4'-thiodiphenol (0.10 mole) is used as the hydroxyaromatic reactant.The reaction temperature is allowed to stabilize at 82° C. and theaqueous sodium hydroxide is added to the clear solution over a 26-minuteperiod. A stirred crystalline slurry forms after 36 minutes of reaction.The reaction continues at 89° C. to 94° C. for a total of 99 minutes.The di(cyano-methylated) product is obtained in 96.2 percent yield ascrystalline plates. A sample of the di(cyano-methylated) product isrecrystallized from methanol providing transparent plates.

Example 8

A reaction is completed using the method of Example 6, except that4,4'-sulfonyldiphenol (0.10 mole) is used as the hydroxyaromaticreactant. The reaction temperature is allowed to stabilized at 87° C.and the aqueous sodium hydroxide is added to the clear solution over a31-minute period. A crystalline slurry forms after 46 minutes ofreaction at 88° C. to 99° C. and the cooling is started. Thedi(cyano-methylated) product is obtained in 96.8 percent yield.

Example 9

A reaction is performed using the method of Example 6, except that1,4-dihydroxybenzene (hydroquinone) (0.10 mole) is used as thehydroxyaromatic reactant. The reaction temperature is allowed tostabilize at 78° C. and the aqueous sodium hydroxide is added to theclear solution over a 27-minute period. The reaction continues at 93° C.to 99° C. for a total of 188 minutes. The reactor is allowed to cool andonce 50° C.-55° C. is reached, a crystalline slurry forms. A washingstep employing 20 percent aqueous sodium hydroxide is employed inaddition to the usual hot water washing. A 77.6 percent yield ofdi(cyano-methylated) product is obtained.

Example 10

A reaction is performed using the method of Example 6, except that2,7-naphthalenediol (0.10 mole) is used as the hydroxyaromatic reactant.The reaction temperature is allowed to stabilize at 75° C. and theaqueous sodium hydroxide is added to the clear solution over a 31-minuteperiod. The reaction continues at 88° C. to 95° C. for a total of 173minutes. The reactor is chilled for 3 hours at 4° C. A washing stepemploying 20 percent aqueous sodium hydroxide is employed in addition tothe usual hot water washing. A 89.2 percent yield ofdi(cyano-methylated) product is obtained.

Example 11

A reaction is performed using the method of Example 6, except that3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol is used as thehydroxyaromatic reactant and 0.80 mole of α-chloroacetonitrile is used.The reaction temperature is allowed to stabilize at 85° C. and theaqueous sodium hydroxide is added to the clear solution over a117-minute period. The reaction continues at 85° C. to 95° C. for atotal of 290 minutes. The reactor is allowed to cool to room temperature(21° C.), the reaction crude is devolatilized to remove unreactedα-chloroacetonitrile and some of the water, and the off-whitedi(cyano-methylated) product is recovered after multiple hot waterwashing in 99.7 percent yield.

Example 12

Forty-one thousandths of a mole of3,3',5,5'-tetrachloro-4,4'-dihydroxybiphenyl, α-chloroacetonitrile (0.40mole) and 60 percent aqueous benzyltrimethylammonium chloride catalyst(0.0164 mole) are added to a reactor under a nitrogen atmosphere. Thereactor is heated to 86° C. then sodium hydroxide (0.123 mole) dissolvedin water (18.5 g) is added to the fine stirred slurry over a 9-minuteperiod. The initial aqueous sodium hydroxide addition induces formationof a clear brown refluxing solution. A crystalline slurry forms after 25minutes of reaction at 95° C. to 97° C. and the cooling is started 3minutes later. After chilling to 4° C. for 30 minutes, filtrationfollowed by washing with 10 percent aqueous sodium hydroxide and hotwater then vacuum drying provides the di(cyano-methylated) product in99.1 percent yield.

Example 13

1,2-Dihydroxybenzene (pyrocatechol) (0.0824 mole), α-chloroacetonitrile(0.4944 mole) and 60 percent aqueous benzyltrimethylammonium chloridecatalyst (0.033 mole) are added with stirring to a reactor under anitrogen atmosphere. The reactor is heated to 94° C. then sodiumhydroxide (0.247 mole), dissolved in water (37.1 g) is added to theclear solution over a 10-minute period. The reaction continues at 93° C.to 94° C. for a total of 113 minutes. After chilling to 4° C. for 1hour, 10 percent aqueous sodium hydroxide and hot water washing thenvacuum drying provides the di(cyano-methylated) product in 70.1 percentyield.

Example 14

A reaction is completed using the method of Example 13, except that1,3-dihydroxybenzene (resorcinol) (0.0824 mole) is used as thehydroxyaromatic reactant. The reaction temperature is allowed tostabilize at 94° C. and the aqueous sodium hydroxide is added to theclear solution over a 24-minute period. The reaction continues at 93° C.to 95° C. for a total of 111 minutes. The di(cyano-methylated) productis obtained in 94.8 percent yield as crystalline plates. Of the threeisomeric dihydroxybenzene reactants employed (see also Examples 9 and13), the highest yield of di(cyano-methylated) product is obtained inthis example using the 1,3-dihydroxy isomer.

Example 15

2,2',4,4'-Tetrahydroxydiphenyl sulfide (0.0824 mole),α-chloroacetonitrile (0.9888 mole) and 60 percent aqueousbenzyltrimethylammonium chloride catalyst (0.066 mole) are added to areactor under a nitrogen atmosphere. The reactor is heated and thestirred slurry becomes a clear solution at room temperature (21° C.).The temperature is allowed to stabilize at 80° C., then 0.494 mole ofsodium hydroxide dissolved in 74.2 g of water is added over a 20-minuteperiod to the stirred solution. The reaction continues at 95° C. for atotal of 92 minutes, after which time a crystalline slurry forms. Afterchilling to 4° C. for 1 hour, filtration followed by washing with 20percent aqueous sodium hydroxide and hot water then vacuum dryingprovides the tetra(cyano-methylated) product in 99.9 percent yield.

Example 16

A novolac oligomer (0.05 mole), α-chloroacetonitrile (0.60 mole) and 60percent aqueous benzyltrimethylammonium chloride catalyst (0.04 mole)are added to a reactor under a nitrogen atmosphere. The novolac oligomerpossesses the following structure where both ortho and para isomericstructures are present: ##STR9## wherein q is an integer and may varyfrom molecule to molecule. Gel permeation chromatography demonstrates anaverage molecular weight of 395. The reactor is heated and the stirredmixture becomes a homogeneous solution at 35° C. The temperature isallowed to stabilize at 98° C., then 0.30 mole of sodium hydroxidedissolved in 45.0 g of water is added over a 12-minute period to thestirred solution. The reaction continues at 95° C. for a total of 145minutes. The reactor is allowed to cool to room temperature (21° C.) andthe product is recovered by extraction into hot chloroform. The combinedchloroform extracts are devolatilized to remove chloroform and therecovered poly(cyano-methylated) oil product is weighed and analyzed bynuclear magnetic resonance spectroscopy. A 92.3 percent isolated yieldof poly(cyano-methylated) product is obtained. Exhaustivecyano-methylation is indicated by the lack of hydroxyl protons in theNMR analysis.

Example 17

One-tenth of a mole of 4,4'-isopropylidenediphenol (sold by The DowChemical Company under the name Parabis® resin intermediate),α-chloroacetonitrile (0.60 mole) and 60 percent aqueousbenzyltrimethylammonium chloride catalyst (0.04 mole) are added to areactor under a nitrogen atmosphere. The reactor is heated and thestirred slurry becomes a clear solution at 32° C. The temperature isallowed to stabilize at 52° C. then 0.40 mole of sodium hydroxidedissolved in 60.0 g of water is added over a 186-minute period to thestirred solution. The reaction continues at 49° C. to 52° C. for a totalof 65 hours. The reactor is allowed to cool to room temperature (22° C.)and the product is recovered by extraction into chloroform. The combinedchloroform extracts are devolatilized to remove chloroform and theremaining oil is washed with 20 percent aqueous sodium hydroxidefollowed by washing with water. The resulting oil is again extractedinto chloroform, dried with anhydrous sodium sulfate, filtered,devolatilized to remove chloroform, weighed, and analyzed by nuclearmagnetic resonance spectroscopy and gas chromatography. A 98.6 percentisolated yield of high purity di(cyano-methylated) product is obtained.

Example 18 (Not an embodiment of the process of this invention)

A reaction is completed using the method of Example 6, except that3,3',5,5'-tetra-t-butyl-4,4'-dihydroxybiphenyl was used as thehydroxyaromatic reactant and 0.80 mole of α-chloroacetonitrile and 0.02mole of 60 percent aqueous benzyltrimethylammonium chloride catalyst areused. The reactor is heated to 101° C. then sodium hydroxide (0.30 mole)dissolved in water (95.0 g) is added to the clear stirred solution overa 6-minute period. A slurry forms after 19 minutes of reaction at 97° C.to 101° C. The reaction continues at 95° C. to 98° C. for a total of 55minutes. Only the unreacted dihydroxyaromatic reactant is recovered.This lack of cyano-methylation is attributed to the steric hindrance ofthe hydroxyl groups induced by the pairs of ortho t-butyl radicals.

II. Variation of the Catalyst Example 19

One-fourth of a mole of 2-chloroacetamide, hydroquinone (0.10 mole),catalyst (0.02 mole) and water (12.8 g) are added with stirring to areactor under a nitrogen atmosphere. The reactor is heated and thestirred slurry becomes a clear light brown solution between thetemperatures of 70° C.-75° C. The temperature is allowed to stabilize at107° C., then 0.40 mole of sodium hydroxide dissolved in 25.0 g of wateris added over a 3-minute period to the stirred solution. After 87.5percent of the sodium hydroxide solution is added, a light tan coloredstirred slurry forms. The reaction continues at 107° C. for a total of 4hours. The reactor is allowed to cool to room temperature (21° C.) andthe slurry is held at this temperature for 3 hours without furtherstirring. The product is filtered and then is vacuum dried at 85° C. for24 hours to a constant weight. The product is then analyzed usingnuclear magnetic resonance spectroscopy (NMR). The results are reportedin Table I.

                  TABLE I                                                         ______________________________________                                        Amido-methylation of Hydroquinone                                                      Product Composition (%)                                                                  Mono-                                                                         (amido-  Di(amido-                                                            methyl-  methyl-                                                              ated)    ated)   Recovered                                           Hydro-   Hydro-   Hydro-  Product                                  Catalyst   quinone  quinone  quinone (g)                                      ______________________________________                                        Benzyltri- none      3.36    96.64   22.3                                     methyl-                                                                       ammonium                                                                      chloride                                                                      Tetrahydroxy-                                                                            9.00     25.00    66.00   18.2                                     methylphos-                                                                   phonium                                                                       chloride                                                                      Tetramethyl-                                                                             3.59     14.87    81.54   22.4                                     ammonium                                                                      chloride                                                                      None*      9.40     15.67    74.92   20.8                                     ______________________________________                                         *Comparative Example  Not an embodiment of this invention.               

The best results are obtained with the benzyltrimethylammonium chloridecatalyst; no unreacted hydroquinone is present in the product and thehighest amount of di(amido-methylated) product is produced.Tetramethylammonium chloride catalysis provides the second highestamount of di(amido-methylated) product and the second lowest amount ofresidual unreacted hydroquinone. The phosphonium halide catalyst,tetrahydroxymethylphosphonium chloride gives an increased amount ofmono(amido-methylated) hydroquinone, thereby unsatisfactorily loweringthe di(amido-methylated) product yield below that of the non-catalyticrun.

Example 20

Two reactions are done using the method of Example 19, except that thereaction temperature is allowed to stabilize at 110° C., then 0.25 moleof sodium hydroxide dissolved in 13.0 g of water is added to the stirredsolution over a 3-minute period. The total reaction time is shortened to0.3 hour at the 110° C. temperature. In one reaction the catalyst isbenzyltrimethylammonium chloride. In the other reaction no catalyst isemployed. The results are reported in Table II.

                  TABLE II                                                        ______________________________________                                                Product Composition (%)                                                                   Mono-                                                                         (amido-  Di(amido-                                                            methyl-  methyl-                                                              ated)    ated)   Recovered                                          Hydro-    Hydro-   Hydro-  Product                                  Catalyst  quinone   quinone  quinone (g)                                      ______________________________________                                        Benzyltri-                                                                               6.81     20.22    72.97   20.7                                     methyl-                                                                       ammonium                                                                      chloride                                                                      None*     12.32     38.12    49.56   18.3                                     ______________________________________                                         *Comparative Example  Not an embodiment of this invention.               

Example 21

A pair of reactions are completed as follows:

(A) One-tenth of a mole of p-chlorophenol, α-chloroacetonitrile (0.30mole) and 60 percent aqueous benzyltrimethylammonium chloride catalyst(0.01 mole) are added to a reactor under a nitrogen atmosphere. Thereactor is heated and the temperature is allowed to stabilize at 81° C.then 0.20 mole of sodium hydroxide dissolved in 30.0 g of water is addedover a 17-minute period to the stirred clear solution. The reactioncontinues at 88° C. to 95° C. for a total of 104 minutes. After chillingto 4° C. for 4 hours, 10 percent aqueous sodium hydroxide and hot waterwashing then vacuum drying provides the cyano-alkylated product inquantitative yield.

(B) A comparative example (Not an embodiment of the process of thisinvention) is completed by adding p-chlorophenol (0.1 mole) andα-chloroacetonitrile to a reactor under a nitrogen atmosphere. Thereactor is heated and the temperature is allowed to stabilize at 55° C.then 0.20 mole of sodium hydroxide dissolved in 30.0 g of water is addedover a 38-minute period to the stirred clear solution. The reactioncontinues at 62° C. to 98° C. for a total of 17.3 hours. The product isanalyzed by gas chromatography demonstrating less than 40 percentconversion of the hydroxyaromatic reactant to the cyano-alkylatedproduct. Substantial unreacted α-chloroacetonitrile is also observed.

The non-catalytic reaction of comparative Example 21(B) stagnates withrespect to conversion resulting in a low yield of the cyano-alkylatedproduct when compared to the catalytic reaction of Example 21(A).

Example 22

A pair of reactions are performed using the method of Example 6, exceptthat 3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol is used as thehydroxyaromatic reactant. In the first reaction, 0.04 mole oftetramethylammonium chloride is used as the catalyst. The reactiontemperature is allowed to stabilize at 75° C. and the aqueous sodiumhydroxide is added to the clear solution over a 33-minute period. Thereaction continues at 75° C. to 97° C. for a total of 146 minutes. Inthe second reaction, only 0.004 mole of tetramethylammonium chloride isused as the catalyst. The reaction temperature is allowed to stabilizeat 82° C. and the aqueous sodium hydroxide is added to the stirredslurry over a 31-minute period. The reaction continues at 75° C. to 96°C. for a total of 107 minutes. The di(cyano-methylated) product isobtained in quantitative yield from the first reaction and 99.4 percentyield from the second reaction.

The efficacy of a range of catalyst loadings is illustrated in thisexample, in spite of the fact that differences in the appearance of thereactant mixture (solution versus slurry) occurs.

Example 23

The reaction of Example 6 is repeated using Dowex® MSA-1 ion-exchangeresin in the chloride form (9.31 g) in place of thebenzyltrimethylammonium chloride catalyst of Example 6. The reactor isheated to 87° C. then sodium hydroxide (0.30 mole) dissolved in water(45.0 g) is added to the fine slurry over a 20-minute period. Theinitial aqueous sodium hydroxide addition induces formation of a clearbrown refluxing solution containing the suspended resin bead catalyst.The reaction continues at 94° C. to 96° C. for a total of 100 minutes.The reaction product is filtered hot to remove the resin bead catalystfollowed by chilling of the filtrate at 4° C. for 1 hour. Washing of thefilter cake with 20 percent aqueous sodium hydroxide and hot water isfollowed by vacuum drying to give the di(cyano-methylated) product in99.2 percent yield.

Example 24

A reaction is performed using the method of Example 6, except that3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol is used as thehydroxyaromatic reactant and tetra-n-butylphosphonium bromide catalyst(0.01 mole) is used in place of the benzyltrimethylammonium chloridecatalyst of Example 6. The reactor is heated to 92° C. and then sodiumhydroxide (0.30 mole) dissolved in water (45.0 g) is added to thestirred clear solution over an 11-minute period. The reaction continuesat 95° C. to 98° C. for a total of 88 minutes. After chilling to 4° C.for 1 hour, filtration followed by washing with 20 percent aqueoussodium hydroxide and hot water then vacuum drying provides thedi(cyano-methylated) product in 99.7 percent yield. The efficacy oftetrasubstituted phosphonium salt catalysts in the cyano-alkylationreactions of this invention is supported via this example.

Example 25

The reaction of Example 17 is repeated using Dowex® MSA-1 ion-exchangeresin in the chloride form (9.31 g) in place of thebenzyltrimethylammonium chloride catalyst of Example 17. The reactor isheated to 85° C. then sodium hydroxide (0.40 mole) dissolved in water(45.0 g) is added to the clear stirred solution containing suspendedresin bead catalyst. The reaction continues at 95° C. to 100° C. for atotal of 127 minutes. The reactor is allowed to cool to room temperature(21° C.), diluted with 100.0 g of water, and extracted with hotchloroform. The combined chloroform extracts are filtered to removesuspended resin bead catalyst then washed with 10 percent aqueous sodiumhydroxide and devolatilized to remove chloroform, weighed, and analyzedby gas chromatography. A 84.1 percent isolated yield of high puritydi(cyano-methylated) product is obtained as an oil.

III. Variation of Alkylating Agent Example 26

A reaction is done using the method of Example 19, except that2-chloropropionamide (0.25 mole) is substituted for 2-chloroacetamide.The catalyst is benzyltrimethylammonium chloride. Thedi(amido-alkylated) product is recovered in 92.4 percent isolated yield.

Example 27

One-tenth of a mole of 3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol,2-chloropropionitrile (0.553 mole) and 60 percent aqueousbenzyltrimethylammonium chloride catalyst (0.04 mole) are added to areactor under a nitrogen atmosphere. The reactor is heated to 80° C.then sodium hydroxide (0.30 mole) dissolved in water (45.0 g) is addedto the stirred clear solution over a 35-minute period. The reactioncontinues at 92° C. to 94° C. for a total of 17 hours. The reactor isallowed to cool and once 80° C. to 85° C. is reached, a viscous oillayer separates. After chilling to 4° C. for 1 hour, the water isdecanted off and 10 percent aqueous sodium hydroxide (200 g) is used towash the oil followed by washing with hot water. A crystalline solidforms after water washing and is recovered by filtration and vacuumdried to provide the di(cyano-alkylated) product in quantitative yield.

Example 28 (Not an embodiment of the process of this invention)

A reaction is done using the method of Example 19, except that3-chloropropionamide (0.25 mole) is substituted for 2-chloroacetamideand the reaction time is increased to 16.3 hours. The catalyst isbenzyltrimethylammonium chloride. No mono- or di(amido-methylated)product was produced.

Example 29 (Not an embodiment of the process of this invention)

A pair of reactions are completed using3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol (0.10 mole) and3-chloropropionitrile (0.60 mole). In the first reaction, 60 percentaqueous benzyltrimethylammonium chloride (0.04 mole) is used as thecatalyst. The reaction temperature is allowed to stabilize at 113° C.and aqueous sodium hydroxide (0.30 mole) dissolved in 45.0 g of water isadded to the clear solution over a 71-minute period. The reactioncontinues at 90° C. to 92° C. for a total of 17 hours. In the secondreaction, tetramethylammonium chloride catalyst (0.02 mole) is used. Thereaction temperature is allowed to stabilize at 94° C. and the aqueoussodium hydroxide is added to the clear solution over a 22-minute period.The reaction continues at 92° C. to 93° C. for a total of 93 minutes.The reaction products are recovered using the method described inExample 6 and analyzed by nuclear magnetic resonance spectroscopy. Onlyunreacted 3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol is recoveredfrom each of these reactions. Considering these results, onlyα-halogenonitrile reactants are suitable for use in the cyano-alkylationreaction of this invention.

Example 30 (Not an embodiment of the process of this invention)

A reaction is completed using the method of Example 29, except that3-bromopropionitrile (0.60 mole) is substituted for3-chloropropionitrile. 60 Percent aqueous benzyltrimethylammoniumchloride (0.04 mole) is used as the catalyst. The reaction temperatureis allowed to stabilize at 91° C. and aqueous sodium hydroxide is addedto the clear solution over a 10-minute period. The reaction continues at94° C. for a total of 21 hours. Only unreacted3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol is recovered from thisreaction.

IV. Miscellaneous Example 31

A pair of reactions are done using the method of Example 19 with thefollowing stoichiometry:

    ______________________________________                                        2-chloroacetamide        2.00 moles                                           hydroquinone             0.50 mole                                            benzyltrimethylammonium chloride                                                                       0.10 mole                                            water                   83.5  g                                               ______________________________________                                    

In both reactions, the temperature is allowed to stabilize at 110° C.,then 2.00 moles of sodium hydroxide dissolved in 125.0 g of water isadded to the stirred solution. In the first reaction, the aqueous sodiumhydroxide is added over a 98-minute period followed by 142 minutes ofreaction. In the second reaction, the aqueous sodium hydroxide is addedover a 3-minute period followed by 237 minutes of reaction. The resultsare reported in Table III.

                  TABLE III                                                       ______________________________________                                                      Product Composition (%)                                                                      Mono-  Di-                                       Sodium          Total        (amido-                                                                              (amido-                                                                              Recov-                             Hydroxide                                                                             Reac-   Reac-   Hy-  methyl-                                                                              methyl-                                                                              ered                               Addition                                                                              tion    tion    dro- ated)  ated)  Prod-                              Time    Time    Time    qui- Hydro- Hydro- uct                                (min)   (min)   (min)   none quinone                                                                              quinone                                                                              (g)                                ______________________________________                                        98      142     240     24.24                                                                              50.51  25.25   83.4                               3      237     240     none  3.14  96.86  109.5                              ______________________________________                                    

Much better diamido-alkylation results are obtained when the NaOH israpidly added; reaction time is greatly reduced.

Example 32 (Not an embodiment of the process of this invention)

The reaction of Example 17 is repeated using Dowex® MSA-1 ion-exchangeresin in the chloride form (9.31 g) and Dowex® MSA-1 ion-exchange resinin the hydroxide form (45.0 g). No alkaline agent is used in thisreaction. The reactor is heated and the clear stirred solutioncontaining suspended resin bead catalyst is held at 93° C. for a totalof 6.4 hours. A series of samples are taken after 1.4, 3.4 and 6.4 hoursof reaction and analyzed by gas chromatography. In every case only about15 percent of the 4,4'-isopropylidenediphenol is converted to productcontaining in excess of 95 percent mono(cyano-methylated) startingmaterial. Substantial unreacted α-chloroacetonitrile is also observed.

Example 33 (Not an embodiment of the process of this invention)

A series of comparative examples illustrative of various prior artmethods are completed as follows:

(A) One-tenth of a mole of 4,4'-isopropylidenediphenol and 1,4-dioxane(70.0 ml) are added to a reactor. The reactor is heated and solidpotassium carbonate (0.20 mole) and water (40.0 g) are added. Heating iscontinued and a clear solution forms at 60° C. The temperature isallowed to stabilize at 75° C., then α-chloroacetonitrile (0.20 mole) isadded over a 5-minute period to the stirred solution. The reactioncontinues at 75° C. for a total of 16 hours. The reactor is allowed tocool to room temperature (22° C.) and the product is devolatilized toremove 1,4-dioxane and some water. Extraction with methyl ethyl ketoneprovides a solution of oil product which is analyzed by gaschromatography, demonstrating about 25 percent conversion of4,4'-isopropylidenediphenol to an 80 percent mono(cyano-methylated) and20 percent di(cyano-methylated) product. Substantial unreactedα-chloroacetonitrile is also observed.

(B) One-tenth of a mole of 4,4'-isopropylidenediphenol and methyl ethylketone (50.0 ml) are added to a reactor. A solution of potassiumcarbonate (0.20 mole) and water (40.0 g) is added and the reactor isheated. Heating is continued and the temperature of the stirred clearsolution is allowed to stabilize at 74° C., then α-chloroacetonitrile(0.50 mole) is added over a 4-minute period. The reaction continues at afinal temperature of 80° C. for a total of 46 hours. A series of samplesare taken after 18, 23, and 46 hours of reaction and analyzed by gaschromatography to provide the following results:

    ______________________________________                                                                mono-                                                                         (cyano-  di(cyano-                                    Sample  4,4'-isopropyl- methyl-  methyl-                                      Time    idenediphenol   ated)    ated)                                        (hr)    (%)             (%)      (%)                                          ______________________________________                                        18      45              45       10                                           23      46              43       11                                           46      38              48       14                                           ______________________________________                                    

Substantial unreacted α-chloroacetonitrile is also observed.

(C) One-tenth of a mole of 4,4'-isopropylidenediphenol and methyl ethylketone (50.0 ml) are added to a reactor. The reactor is heated and asolution of sodium hydroxide (0.20 mole) and water (80.0 g) is added.Heating is continued and the temperature of the stirred clear solutionis allowed to stabilize at 76° C., then α-chloroacetonitrile (0.30 mole)is added over a 14-minute period. The reaction continues at a finaltemperature of 80° C. for a total of 25.5 hours. A series of samples aretaken after 16.5, 21.5 and 25.5 hours of reaction and analyzed by gaschromatography to provide the following results:

    ______________________________________                                                                mono-                                                                         (cyano-  di(cyano-                                    Sample  4,4'-isopropyl- methyl-  methyl-                                      Time    idenediphenol   ated)    ated)                                        (hr)    (%)             (%)      (%)                                          ______________________________________                                        16.5    50              44       6                                            21.5    50              44       6                                            25.5    51              44       5                                            ______________________________________                                    

Substantial unreacted α-chloroacetonitrile is also observed.

(D) One-tenth of a mole of 4,4'-isopropylidenediphenol andα-chloroacetonitrile (0.80 mole) are added to a reactor. The reactor isheated and a clear solution forms at 56° C. The temperature is allowedto stabilize at 80° C., then a solution of sodium hydroxide (0.20 mole)and water (40.0 g) is added over a 68-minute period. The reactioncontinues at 80° C. for a total of 6.75 hours. Samples are taken after 4and 6.75 hours of reaction and analyzed by gas chromatography to providethe following results:

    ______________________________________                                                                mono-                                                                         (cyano-  di(cyano-                                    Sample  4,4'-isopropyl- methyl-  methyl-                                      Time    idenediphenol   ated)    ated)                                        (hr)    (%)             (%)      (%)                                          ______________________________________                                        4.0     7.5             37       55.5                                         6.75    1.0             39       60.0                                         ______________________________________                                    

Substantial unreacted α-chloroacetonitrile is also observed.

(E) A reaction is completed using the method of Example 33(D), exceptthat a solution of sodium hydroxide (0.20 mole) and water (15.0 g) isadded over a 37-minute period. The reaction time is increased to a totalof 84 hours. A sample is taken after 84 hours of reaction and analyzedby gas chromatography to provide the following results:

    ______________________________________                                                                mono-                                                                         (cyano-  di(cyano-                                    Sample  4,4'-isopropyl- methyl-  methyl-                                      Time    idenediphenol   ated)    ated)                                        (hr)    (%)             (%)      (%)                                          ______________________________________                                        84      4               37       59                                           ______________________________________                                    

Substantial unreacted α-chloroacetonitrile is also observed.

(F) A reaction is completed using the method of Example 33(D), exceptthat a solution of sodium hydroxide (0.40 mole) and water (60.0 g) isadded over a 52-minute period. After 23 hours of reaction at 80° C., thereaction temperature is increased to 100° C. The total reaction time is46.5 hours. A pair of samples are taken after 6.33 and 46.5 hours ofreaction and analyzed by gas chromatography to provide the followingresults:

    ______________________________________                                                                mono-                                                                         (cyano-  di(cyano-                                    Sample  4,4'-isopropyl- methyl-  methyl-                                      Time    idenediphenol   ated)    ated)                                        (hr)    (%)             (%)      (%)                                          ______________________________________                                         6.33   1               16       83                                           46.5    1               17       82                                           ______________________________________                                    

Substantial unreacted α-chloroacetonitrile is also observed.

(G) A reaction is completed using the method of Example 33(D), exceptthat the reaction temperature is allowed to stabilize at 92° C. then asolution of sodium hydroxide (0.40 mole) and potassium iodide catalyst(0.04 mole) in water (70.0 g) is added over a 40-minute period. Thereaction continues at a final temperature of 98° C. for 16 hours.Analysis of the product by gas chromatography provides the followingresults:

    ______________________________________                                                                mono-                                                                         (cyano-  di(cyano-                                    Sample  4,4'-isopropyl- methyl-  methyl-                                      Time    idenediphenol   ated)    ated)                                        (hr)    (%)             (%)      (%)                                          ______________________________________                                        16      1               17       82                                           ______________________________________                                    

Substantial unreacted α-chloroacetonitrile is also observed.

The chemistry of each of these comparative examples provides mixturescontaining mono and di(cyano-methylated) products and unreacted4,4'-isopropylidenediphenol. All of these reactions stagnate withrespect to conversion, resulting in comparatively low yields of thedi(cyano-methylated) product.

Example 34 (Not an embodiment of the process of this invention)

One-tenth of a mole of 3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenoland 0.40 mole of sodium hydroxide dissolved in 120.0 g of water arereacted under a nitrogen atmosphere to produce the disodium salt. Thetemperature of the clear solution is allowed to stabilize at 80° C. then0.04 mole of tetramethylammonium chloride catalyst is added inducingslurry formation. α-Chloroacetonitrile (0.30 mole) is added over a13-minute period. The initial α-chloroacetonitrile addition inducesformation of a clear pale yellow refluxing solution. The reactioncontinues at 92° C.-95° C. for a total of 95 minutes. The organic layeris resolved and solidifies to a light amber solid at room temperature.This solid is dried under vacuum to a constant weight and analyzed bygas chromatography demonstrating the presence of 6 percent unreacted3,3',5,5'-tetrabromo-4,4'-isopropylidenediphenol, 25 percentmono(cyano-methylated) product and 69 percent di(cyano-methylated)product.

When compared to Examples 11 and 22, the mode of reaction described inthis example whereby the phenate is preformed provides incompleteconversion of hydroxyaromatic reactant and less di(cyano-methylated)product.

Example 35 (Not an embodiment of the process of this invention)

A comparative example illustrative of the prior art cyano-ethylation iscompleted as follows:

The novolac oligomer described in Example 16 (204 g), acrylonitrile (636g) and 50 percent aqueous benzyltrimethylammonium hydroxide (24 g) arerefluxed at 76° C. for 24 hours. The isolated product contains only 50percent cyano-ethylation based on phenolic titration. Considering theseresults, the prior art Michael addition of acrylonitrile tohydroxyaromatic reactants is not effective in producing apoly(cyano-ethylated) product.

V. Use of Partially Amido-alkylated Compositions in the Preparation ofEpoxy Resins Example 36 A. Synthesis of partially amido-methylatednovolac:

A portion (235.68 g, 1.00 mole hydroxyl groups) of a phenol formaldehydecondensation product (novolac) possessing an average functionality of2.2, 2-chloroacetamide (102.86 g, 1.10 moles) and 60 percent aqueousbenzyltrimethylammonium chloride (15.48 g, 0.05 mole active) are addedto a reactor and are heated to a 125° C. solution maintained under anitrogen atmosphere with stirring. At this time, sodium hydroxide (44.0g, 1.10 moles) previously dissolved in 44.0 g of deionized water isadded to the reactor over a 2-minute period inducing a maximum exothermof 132° C., followed by cooling to 115° C. The 115° C. reactiontemperature is maintained for 173 minutes, then deionized water (200 g)is added to the reactor, followed by acidification with 1.0 normalhydrochloric acid to a pH of 5 and cooling to room temperature (25° C.).The reaction product is extracted with two 200-g portions ofmethylisobutyl ketone, then the combined extracts are dried overanhydrous sodium sulfate. After filtration, the solvent is removed byrotary evaporation under vacuum at 100° C. until a constant productweight (230.1 g) is obtained. A portion of the tacky, transparent, lightyellow colored solid product is analyzed by nuclear magnetic resonancespectroscopy, indicating that 44 percent of the --OH groups areconverted to ##STR10## groups.

B. Copolymerization of partially amido-methylated novolac and an epoxyresin:

A portion (4.77 g) of partially amido-methylated novolac from Example36A, a diglycidylether of bisphenol A possessing an epoxide equivalentweight of 186 (10.0 g) and propylene gylcol monomethylether (14.77 g)are combined to form a solution. The solution is catalyzed by additionof 2.0 g of 5 percent by weight 2-methylimidazole in propylene glycolmonomethylether, and then is used to run stroke cures. The results arereported in Table IV.

                  TABLE IV                                                        ______________________________________                                        Cure Temperature (°C.)                                                                   Gel Time (sec)                                              ______________________________________                                        150               165                                                         175               58                                                          200               24                                                          ______________________________________                                    

Example 37 (Not an embodiment of this invention) Copolymerization ofnovolac and an epoxy resin:

A portion (6.70 g) of the same novolac used as a reactant in Example36A, a diglycidyl ether of bisphenol A possessing an epoxide equivalentweight of 186 (10.0 g) and propylene glycol monomethylether (16.7 g) arecombined to form a solution. The solution is catalyzed by addition of2.00 g of 5 percent by weight 2-methylimidazole in propylene glycolmonomethylether, and then is used to run stroke cures. The results arereported in Table V.

                  TABLE V                                                         ______________________________________                                        Cure Temperature (°C.)                                                                   Gel Time (sec)                                              ______________________________________                                        150               241                                                         175               96                                                          200               37                                                          ______________________________________                                    

Comparing the results of Tables IV and V, it can be seen that the use ofthe partially amido-alkylated material provides a faster cure than thenonamido-alkylated material.

Example 38

The unused partially amido-methylated novolac, epoxy resin and catalystsolution from Example 36B is used to coat a 20 gauge, unpolished, coldrolled, steel plate with a number 28 draw down bar. Curing is completedat 175° C. for 15 minutes (900 sec) in a forced-air, convection-typeoven. The cured plate is recovered with a glossy smooth flaw-free finishand is tested for pencil hardness, methyl ethyl ketone double rubs andreverse impact strength using a Gardener drop weight impact tester. Theresults are reported in Table VI.

Example 39 (Not an embodiment of this invention)

The unused novolac, epoxy resin and catalyst solution from Example 37 isused to coat a steel plate using the method of Example 38. The curedplate is tested using the method of Example 38. The results are reportedin Table VI.

                  TABLE VI                                                        ______________________________________                                                         Ex. 38                                                                              Ex. 39                                                 ______________________________________                                        Pencil Hardness    4H      4H                                                 Methyl ethyl ketone                                                                              >200    89                                                 Double Rubs                                                                   Reverse Impact     >160    >160                                               Strength (ft-lb)                                                              ______________________________________                                    

Use of the partially amido-alkylated composition gives a cured resinhaving improved resistance to methyl ethyl ketone.

What is claimed is:
 1. A composition comprising a compound representedby the formula: ##STR11## wherein each Ar' independently is mono-orpolyvalent organic radical selected from moieties having from 1 to about2 aromatic rings, n' is individually selected from 0, 1 or 2, with theproviso that at least one n' is not zero, q is at least 0.001; R' isindependently a divalent hydrocarbon moiety having from 1 to about 3carbon atoms or a ##STR12## group, wherein z has a value of from zero toabout 10; and Q is independently H or (CR₁ R₂)Y with the proviso thatnot all Q moieties are H and Y is --C.tbd.N and wherein R₁ and R₂ areindependently H or C₁ -C₁₀ alkyl.
 2. The composition of claim 1 whereineach Q is --CR₁ R₂ --CN.
 3. The composition of claim 1 wherein at leastone Q is --CR₁ R₂ --CN.
 4. A composition comprising compoundsrepresented by the formula ##STR13## wherein q is at least about 0.001;Y is --C.tbd.N wherein each R' is independently a divalent hydrocarbonmoiety having from 1 to about 3 carbon atoms or a ##STR14## group,wherein z has a value of from zero to about 10.